CN102348728A - Polymer, organic thin film comprising the polymer, and organic thin-film element including same - Google Patents

Polymer, organic thin film comprising the polymer, and organic thin-film element including same Download PDF

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CN102348728A
CN102348728A CN2010800112702A CN201080011270A CN102348728A CN 102348728 A CN102348728 A CN 102348728A CN 2010800112702 A CN2010800112702 A CN 2010800112702A CN 201080011270 A CN201080011270 A CN 201080011270A CN 102348728 A CN102348728 A CN 102348728A
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家裕隆
吉村笃轨
安苏芳雄
上田将人
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Osaka University NUC
Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Abstract

A polymer having a low LUMO, high charge-transporting properties, and high solubility in solvents. The polymer has a repeating unit represented by formula (I). [In formula (I), Ar0 represents an optionally substituted aromatic ring or an optionally substituted heterocycle, and X1 and X2 are the same or different and each represents an oxygen atom or a sulfur atom.]

Description

Polymkeric substance, used the organic film of this polymkeric substance and had its organic thin film device
Technical field
The present invention relates to polymkeric substance and monomer, and the organic film that has used polymkeric substance, have its organic thin film device, OTFT, organic solar batteries and optical sensor.
Background technology
As organic transistor, organic solar batteries, the material of the organic thin film device of optical sensor etc. has been developed the various compounds with conjugacy of organic n type, semiconductor material that are.As these concrete examples with compound of conjugacy, the end that has proposed on main chain, to have the oligo-thiophenes of thiphene ring imports the compound (patent documentation 1) of fluoroalkyl.
[prior art document]
[patent documentation]
No. 2003/010778 brochure of [patent documentation 1] International Publication
Summary of the invention
[problem that invention will solve]
Used the organic thin film device of organic semiconductor material preferably to have high charge transfer property,, hoped that LUMO is also low except having high conjugacy in order to obtain charge transfer property.But, from the practicability viewpoint of organic thin film device, not only need the charge transfer property of organic semiconductor material high, also requirement can form good organic film at an easy rate.If organic semiconductor material has the high resolution to solvent; Then can easily form the film of big area, homogeneous through coating; But the compound with conjugacy in the past has solvability in the solvent low-down trend that becomes when realizing especially low LUMO.
Therefore, the present invention researches and develops in view of such thing, and its purpose is to provide a kind of low LUMO, and has high charge transfer property, and solvent is shown the polymkeric substance of high resolution.The present invention also aims to, be provided for obtaining the monomer of this polymkeric substance, and the organic film that has used polymkeric substance, the OTFT of this organic film had, organic solar batteries, the organic thin film device that optical sensor is such.
[solving the method for problem]
To achieve these goals, polymkeric substance of the present invention is characterised in that to have the represented repeating unit of formula (I).
Figure BDA0000090305410000021
[in the formula, Ar 0Expression can have substituent aromatic nucleus maybe can have substituent heterocycle, X 1And X 2Can be identical or different, expression Sauerstoffatom or sulphur atom.]
In the polymkeric substance of the invention described above, pendant moiety contained in the represented repeating unit of formula (I) is through having X 1, X 2And forming low LUMO, this pendant moiety is owing to have based on X in addition 1, X 2Two keys of institute's bonded and Ar 0The conjugated structure of represented structure is so pendant moiety integral body has high conjugacy.Therefore, polymkeric substance of the present invention can be brought into play excellent electric charge transmission property.In addition, owing to partly form the softish structure with the main chain bonded, think has the polymkeric substance of high resolution to solvent.
In the polymkeric substance of the present invention, the represented repeating unit of formula (I) is preferably the represented repeating unit of formula (I-a).Through having such repeating unit, polymkeric substance except side chain with lower LUMO and high conjugacy, the trend that also has solvability to become higher.
Figure BDA0000090305410000031
[in the formula, X 1And X 2With above-mentioned synonym, Ar 1And Ar 2Can be identical or different, the aromatic hydrocarbyl that expression can have the divalent of substituent carbon number more than 6 maybe can have the heterocyclic radical of the divalent of substituent carbon number more than 4; R 1And R 2Can be identical or different, the group of expression hydrogen atom, halogen atom or 1 valency; M and n can be identical or different, are 0～6 integer; Z 1Represent following formula (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) with (ix) (below be called " (i)～(ix) ") represented group in any, the R in these formulas 3, R 4, R 5And R 6Can be identical or different, the group of expression hydrogen atom or 1 valency, R 3And R 4Can interosculate and form ring; The (iv) represented group of following formula can about counter-rotating; In addition, Ar 1Or Ar 2There are when a plurality of a plurality of Ar 1Or Ar 2Can be identical or different.]
Figure BDA0000090305410000032
Improve the viewpoint of charge transfer property from further raising conjugacy, in the formula (I-a), Ar 1And Ar 2Can be identical or different, the represented group of preferred formula (II).
Figure BDA0000090305410000041
[in the formula, R 7And R 8Can be identical or different, the group of expression hydrogen atom or 1 valency, Z 2Expression (xi), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii) and (xix) represented arbitrary group, the R in the above-mentioned formula 9, R 10, R 11And R 12Can be identical or different, the group of expression hydrogen atom or 1 valency, R 9And R 10Can interosculate forms ring, the represented group of formula (xiv) can about counter-rotating.]
And then, in the formula (I-a), Z 1Be preferably the (ii) represented group of formula, in the formula (II), Z 2Be preferably the represented group of formula (xii).Polymkeric substance with these structures can be brought into play more excellent electric charge transmission property.
In addition, the R in the formula (I-a) 1And R 2At least one side be preferably the represented group of formula (III).Have above-mentioned group through end, can realize lower LUMOization, thereby can obtain excellent electric charge transmission property more at pendant moiety.
Figure BDA0000090305410000051
[in the formula, Ar 3The aromatic hydrocarbyl that expression can have substituent 3 valencys maybe can have the heterocyclic radical of substituent 3 valencys, Y 1And Y 2Can be identical or different, expression Sauerstoffatom, the represented group of sulphur atom or formula (a).]
Figure BDA0000090305410000052
[in the formula, A 1And A 2Can be identical or different, the group of expression hydrogen atom, halogen atom or 1 valency, A 1And A 2In at least one, be the group of electrophilic property.]
Be preferably the represented base of formula (III), the represented group of formula (IV) especially.
Figure BDA0000090305410000053
[in the formula, Y 3And Y 4Can be identical or different, expression Sauerstoffatom, the represented group of sulphur atom or formula (a), R 0The group of expression hydrogen atom or 1 valency, j is to R from 1 0The integer that institute's bonded ring is had between can substituted positional number.R 0Exist when a plurality of, they can be identical or different.Z 3Expression (xxi), (xxii), (xxiii), (xxiv), (xxv), (xxvi), (xxvii), (xxviii) and (xxix) any in the represented group, the R in these formulas 13, R 14, R 15And R 16Can be identical or different, the group of expression hydrogen atom or 1 valency, R 13And R 14Can interosculate forms ring, the represented group of formula (xxiv) can about counter-rotating.]
In addition, the present invention provides formula (XI) represented monomer.This monomer of the present invention can easily form the polymkeric substance of the invention described above through polymerization, and low LUMO and charge transfer property are excellent for forming, and has the polymkeric substance of the high resolution in solvent very useful.
Figure BDA0000090305410000062
[in the formula, Ar 0Expression can have substituent aromatic nucleus maybe can have substituent heterocycle, X 1And X 2Can be identical or different, expression Sauerstoffatom or sulphur atom.]
Monomer of the present invention further is preferably the represented monomer of formula (XI-a).Through such monomer, can easily obtain than above-mentioned polymkeric substance preferably.
Figure BDA0000090305410000071
[in the formula, Ar 1And Ar 2Can be identical or different, the aromatic hydrocarbyl of the divalent of expression carbon number more than 6 or the heterocyclic radical of the divalent of carbon number more than 4, R 1And R 2Can be identical or different, the group of expression hydrogen atom, halogen atom or 1 valency, X 1And X 2Can be identical or different, expression Sauerstoffatom or sulphur atom.M and n can be identical or different, are 0～6 integer.Z 1Expression (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) with (ix) represented group in any, the R in the above-mentioned formula 3, R 4, R 5And R 6Can be identical or different, the group of expression hydrogen atom or 1 valency, R 3And R 4Can interosculate forms ring, the (iv) represented group of formula can about counter-rotating.In addition, Ar 1Or Ar 2There are when a plurality of a plurality of Ar 1Or Ar 2Can be identical or different.]
Figure BDA0000090305410000072
The present invention also provides the organic film of the polymkeric substance that contains the invention described above.Organic film of the present invention is owing to contain the polymkeric substance of the invention described above, except having high charge transfer property, can also be based on coating film forming, and the film and various organic film that therefore big area can be provided and have the characteristic of homogeneous with this organic film.
Particularly; The present invention provides a kind of OTFT; It has source electrode and drain electrode, as the organic semiconductor layer of the current path between them and control gate electrode through the magnitude of current of above-mentioned current path, organic semiconductor layer is made up of organic film of the present invention.Such OTFT because organic semiconductor layer is made up of organic film of the present invention, therefore can be brought into play high charge transfer property, as transistor, has high-performance.
In addition, the present invention provides the organic solar batteries and the optical sensor of the organic film with the invention described above.These organic thin film devices so can obtain the transmission property of the required electric charge of the action of each element well, can be brought into play excellent characteristic owing to also have organic film of the present invention.
[effect of invention]
According to the present invention, can be provided as low LUMO and have high charge transfer property, and solvent is shown the polymkeric substance of high resolution.In addition, can also be provided for obtaining the monomer of this polymkeric substance, and the organic film that has used polymkeric substance, have OTFT, organic solar batteries, these organic thin film devices of optical sensor of this organic film.
Description of drawings
Fig. 1 is the constructed profile of the OTFT of the 1st embodiment.
Fig. 2 is the constructed profile of the OTFT of the 2nd embodiment.
Fig. 3 is the constructed profile of the OTFT of the 3rd embodiment.
Fig. 4 is the constructed profile of the OTFT of the 4th embodiment.
Fig. 5 is the constructed profile of the OTFT of the 5th embodiment.
Fig. 6 is the constructed profile of the OTFT of the 6th embodiment.
Fig. 7 is the constructed profile of the OTFT of the 7th embodiment.
Fig. 8 is the constructed profile of the solar cell of embodiment.
Fig. 9 is the constructed profile of the optical sensor of the 1st embodiment.
Figure 10 is the constructed profile of the optical sensor of the 2nd embodiment.
Figure 11 is the constructed profile of the optical sensor of the 3rd embodiment.
Embodiment
Below, according to circumstances, preferred embodiment at length illustrate of the present invention with reference to accompanying drawing.In addition, for the explanation of accompanying drawing,, omit the multiple explanation for same element annotation prosign.In addition, the position relation that waits up and down is based on position shown in the drawings relation.And then the dimensional ratios of accompanying drawing is not limited by illustrated ratio.
[polymkeric substance]
The polymkeric substance of this embodiment has the represented repeating unit of formula (I).This polymkeric substance uses so can be used as organic n N-type semiconductorN owing to have high (pi-conjugated system) pendant moiety of conjugacy.In addition, partly have the high structure of flexibility,, can use solution to form essentially homogenous organic film so the solvability in solvent is excellent with the main chain bonded.Therefore, has high performance organic thin film device through using such polymkeric substance, can making.
In the formula (I), Ar 0Expression can have substituent aromatic nucleus maybe can have substituent heterocycle.X 1And X 2Can be identical or different, expression Sauerstoffatom or sulphur atom are preferably Sauerstoffatom.
As Ar 0Aromatic nucleus, can enumerate phenyl ring, condensed ring, the aromatic nucleus of preferred carbon number 6～60, the more preferably aromatic nucleus of carbon number 6～20.As condensed ring, can enumerate naphthalene nucleus, anthracene nucleus, tetracene ring, pentacene ring, pyrene Huan 、 perylene ring, fluorenes ring.As the substituting group that aromatic nucleus can have, can enumerate halogen atom, saturated or unsaturated alkyl, aryl, alkoxyl group, aryloxy, the heterocyclic radical of 1 valency, amino, nitro, cyanic acid.
As heterocycle, the heterocycle of preferred carbon number 4～60, more preferably 4～20 heterocycle.As such heterocycle, can enumerate thiophene, thienothiophene, two thienothiophenes, thiazole, pyrroles, pyridine, pyrimidine etc.As the substituting group that heterocycle can have, can enumerate the same group of substituting group that can have with above-mentioned aromatic nucleus.
The represented repeating unit of formula (I) is preferably the represented repeating unit of formula (I-a).
Figure BDA0000090305410000101
In the formula (I-a), X 1And X 2With above-mentioned synonym.Ar 1And Ar 2Can be identical or different, the aromatic hydrocarbyl that expression can have the divalent of substituent carbon number more than 6 maybe can have the heterocyclic radical of the divalent of substituent carbon number more than 4, R 1And R 2Can be identical or different, the group of expression hydrogen atom, halogen atom or 1 valency.M and n can be identical or different, are 0～6 integer, preferred 0～3 integer, more preferably 0～1 integer.From the viewpoint of the easness of the manufacturing of polymkeric substance, preferred especially m=n.In addition, Ar 1Or Ar 2There are when a plurality of a plurality of Ar 1Or Ar 2Can be identical or different.
In the formula (I-a), Z 1Expression (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) with (ix) represented group in any, the R in the above-mentioned formula 3, R 4, R 5And R 6Can be identical or different, the group of expression hydrogen atom or 1 valency, R 3And R 4Can interosculate forms ring, the (iv) represented group of formula can about counter-rotating.
Z 1In the represented group of expression (i)～(ix) any, preferred formula (ii), (iii), (v), (and viii) with (ix) represented group in any, further preferred formula is (ii), (iii) and (any in the v) represented group.Wherein, the special (ii) represented group of preferred formula.Contain Z 1The ring structure of part be thiphene ring, when furan nucleus and pyrrole ring, during in particular for thiphene ring, the electrical properties of indicating characteristic property can expect that it embodies the new electrology characteristic that did not in the past have.
R in the formula (I-a) 1And R 2Can be identical or different, be the group of hydrogen atom, halogen atom or 1 valency.In addition, R 3, R 4, R 5And R 6Can be identical or different, be the group of hydrogen atom or 1 valency.As R 1And R 2Halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms and iodine atom.
In addition, as R 1～R 6The group of 1 valency; The group that constitutes for low molecular chain by straight chain shape or branched; (can be monocycle also can be condensed ring can to enumerate the cyclic group of 1 valency of carbon number 3～60; Can be that carbocyclic ring also can be a heterocycle; Can be saturated also can be unsaturated, can have substituting group); Saturated or unsaturated alkyl; Hydroxyl; Alkoxyl group; Alkyloyl oxygen base; Amino; The oxygen base is amino; Alkylamino; Dialkyl amido; Alkanoylamino; Cyanic acid; Nitro; Alkylsulfonyl; Can be by the substituted alkyl of halogen atom; Alkoxyl group alkylsulfonyl (alkoxyl group can be replaced by halogen atom); Alkyl sulphonyl (alkyl can be replaced by halogen atom); Sulfamyl; Alkylsulfamoyl group; Carboxyl; Formamyl; Alkyl-carbamoyl; Alkyloyl and alkoxy carbonyl.
As saturated hydrocarbyl, can enumerate the straight chain shape of carbon number 1～20, branched or cyclic alkyl, straight chain shape, branched or the cyclic alkyl of preferred carbon number 1～12.As alkyl, can lift methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, 3-methyl butyl, amyl group, hexyl, 2-ethylhexyl, heptyl, octyl group, nonyl, decyl, lauryl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, cyclo-dodecyl.In addition, as the alkyl in the group that contains alkyl in its structure (for example, alkoxyl group, alkylamino, alkoxy carbonyl), can enumerate and above-mentioned same group.
As unsaturated alkyl, can enumerate vinyl, 1-propenyl, allyl group, propargyl, pseudoallyl, 1-butylene base and crotyl.
As alkyloyl, can enumerate formyl radical, ethanoyl, propionyl, isobutyryl, pentanoyl and isovaleryl etc.In addition, as the alkyloyl in the group that in its structure, contains alkyloyl (for example, alkyloyl oxygen base, alkanoylamino), can enumerate and above-mentioned same group.In addition, the alkyloyl of carbon number 1 is meant formyl radical, for for the group that contains alkyloyl in its structure, too.
As R 1And R 2, wherein, preferred hydrogen atom, fluorine atom, the alkyl of carbon number 1～20, the fluoroalkyl of carbon number 1～20, the alkoxyl group of carbon number 1～20, the Fluoroalkyloxy of carbon number 1～20, the more preferably fluoroalkyl of the alkyl of hydrogen atom, fluorine atom, carbon number 1～20, carbon number 1～20.
And then, the lumo energy of polymkeric substance is reduced, from improving the viewpoint of charge transfer property, R 1And R 2At least one side be preferably the represented group of formula (III).
Figure BDA0000090305410000121
In the formula (III), Ar 3The aromatic hydrocarbyl that expression can have substituent 3 valencys maybe can have the heterocyclic radical of substituent 3 valencys, Y 1And Y 2Can be identical or different, expression Sauerstoffatom, the represented group of sulphur atom or formula (a).
In the formula (a), A 1And A 2Can be identical or different, the group of expression hydrogen atom, halogen atom or 1 valency, A 1And A 2In at least one for the group of electrophilic property.
As the Ar in the formula (III) 3The aromatic hydrocarbyl of 3 valencys, be meant from phenyl ring or condensed ring and remove 3 hydrogen atoms and remaining atomic group that be preferably carbon number 6～60, more preferably carbon number 6～20.As condensed ring, can enumerate and above-mentioned Ar 0Same situation.As the aromatic hydrocarbyl of 3 valencys, preferably remove 3 hydrogen atoms and remaining atomic group from phenyl ring, fluorenes ring.The aromatic hydrocarbyl of 3 valencys can have substituting group, at this moment, in the carbon number of the aromatic hydrocarbyl of 3 valencys, does not comprise substituent carbon number.As substituting group, can enumerate halogen atom, saturated or unsaturated alkyl, aryl, alkoxyl group, aryloxy, the heterocyclic radical of 1 valency, amino, nitro, cyanic acid.
In addition, the heterocyclic radical of so-called 3 valencys is meant from the hetero ring type compound and removes 3 hydrogen atoms and remaining atomic group that carbon number is generally 3～60, preferred 3～20.As the hetero ring type compound, can enumerate and above-mentioned Ar 0The material that situation is same.As the heterocyclic radical of 3 valencys, preferably remove 2 hydrogen atoms and remaining atomic group from thiophene, thienothiophene.The heterocyclic radical of 3 valencys also can have substituting group, at this moment, in the carbon number of the heterocyclic radical of 3 valencys, does not comprise substituent carbon number.As substituting group, can enumerate halogen atom, saturated or unsaturated alkyl, aryl, alkoxyl group, aryloxy, the heterocyclic radical of 1 valency, amino, nitro, cyanic acid.
As the A in the formula (a) 1And A 2Halogen atom, the group of 1 valency, can enumerate and above-mentioned R 1And R 2The same group of situation.In addition, as the group of electrophilic property, but illustration cyanic acid, nitro, aldehyde radical, acyl group, alkoxy carbonyl, carboxyl, hydroxyl, halogen atom, preferred cyanic acid, nitro, halogen atom, preferred especially cyanic acid.Pass through A 1And A 2At least one side be the group of electrophilic property, can fall LUMO lower.
As the represented base of formula (III), the special represented base of preferred formula (IV).
Figure BDA0000090305410000141
In the formula, Y 3And Y 4Can be identical or different, be Sauerstoffatom, the represented base of sulphur atom or formula (a) is preferably Sauerstoffatom.R 0The group of expression hydrogen atom or 1 valency, j is to R from 1 0The integer that institute's bonded ring is had between can substituted positional number.R 0Exist when a plurality of, they can be identical or different.Z 3In the represented group of expression (xxi)～(xxix) any, the R in the above-mentioned formula 13, R 14, R 15And R 16Can be identical or different, the group of expression hydrogen atom or 1 valency, R 13And R 14Can interosculate forms ring, the represented group of formula (xxiv) can about counter-rotating.
Z in the formula (IV) 3Preferred formula (xxii), (xxiii), (xxv), (xxviii) and any represented base (xxix), more preferably formula (xxii), (xxiii) and any represented group (xxv), the further represented group of preferred formula (xxii).Contain Z 3Ring when being thiphene ring, furan nucleus and pyrrole ring, during in particular for thiphene ring, the electrical properties of indicating characteristic can be expected the new electrology characteristic that its performance did not have in the past.
In addition, as R 0, R 13～R 16The group of 1 valency, can use with as above-mentioned R 1And R 2And the same group of group of 1 valency that illustrates.
Thus, as the R in the formula (I-a) 1Or R 2Represented group, through the represented base of the formula (III) with the group that contains electrophilic property (the represented base of preferred formula (IV)), intermolecular, the group of electrophilic property becomes each other and is easy to interact.Consequently, polymkeric substance can be used as the good organic n N-type semiconductorN performance function of charge transfer property.
And then, in formula (I-a), Ar 1And Ar 2Can be identical or different, be the aromatic hydrocarbyl of the divalent of carbon number more than 6 or the heterocyclic radical of the divalent of carbon number more than 4, they can have substituting group.
So-called Ar 1Or Ar 2The aromatic hydrocarbyl of represented divalent is meant the atomic group of removing the remnants of 2 hydrogen atoms from phenyl ring or condensed ring, preferred carbon number 6～60, more preferably 6～20.As condensed ring, can enumerate naphthalene nucleus, anthracene nucleus, tetracene ring, pentacene ring, pyrene Huan 、 perylene ring, fluorenes ring.Wherein, as the aromatic hydrocarbyl of divalent, preferably remove 2 hydrogen atoms and remaining atomic group from phenyl ring, pentacene ring, pyrene ring or fluorenes ring.In addition, in the carbon number of the aromatic hydrocarbyl of divalent, do not comprise substituent carbon number.As substituting group, can enumerate halogen atom, saturated or unsaturated alkyl, aryl, alkoxyl group, aryloxy, the heterocyclic radical of 1 valency, amino, nitro, cyanic acid.
In addition, so-called Ar 1Or Ar 2The heterocyclic radical of represented divalent is meant from the hetero ring type compound and removes 2 hydrogen atoms and remaining atomic group, preferred carbon number 4～60, and more preferably carbon number 4～20.Here, so-called hetero ring type compound is meant in the organic compound with ring type structure, and the element that constitutes ring is a carbon atom not only, also comprises heteroatomic compounds such as oxygen, sulphur, nitrogen, phosphorus, boron, silicon in the ring.
Heterocyclic radical as divalent; Can enumerate from thiophene, thienothiophene, two thienothiophenes, thiazole, pyrroles, pyridine, pyrimidine and remove 2 hydrogen atoms and remaining atomic group, preferably remove 2 hydrogen atoms and remaining atomic group from thiophene, thienothiophene, thiazole.In addition, in the carbon number of the heterocyclic radical of divalent, do not comprise substituent carbon number.As substituting group, can enumerate halogen atom, saturated or unsaturated alkyl, aryl, alkoxyl group, aryloxy, the heterocyclic radical of 1 valency, amino, nitro, cyanic acid.
As Ar 1And Ar 2, the special represented base of preferred formula (II).
Figure BDA0000090305410000161
In the formula, R 7And R 8Can be identical or different, the group of expression hydrogen atom or 1 valency, Z 2Expression (xi), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii) and (xix) any in the represented group, the R in the above-mentioned formula 9, R 10, R 11And R 12Can be identical or different, the group of expression hydrogen atom or 1 valency, R 9And R 10Can interosculate forms ring, the represented group of formula (xiv) can about counter-rotating.
Figure BDA0000090305410000162
Z in the formula (II) 2Be preferably formula (xii), (xiii), (xv), (xviii) and (xix) in any represented group, more preferably formula (xii), (xiii) and (xv) in any represented group, the further represented group of preferred formula (xii).Contain Z 2The ring of part when being thiphene ring, furan nucleus and pyrrole ring, during in particular for thiphene ring, the electrical properties of indicating characteristic can be expected the new electrology characteristic that its performance did not have in the past.
In addition, as R 7～R 12The group of 1 valency, can use with as above-mentioned R 1And R 2The same group of group of 1 shown valency.
In the polymkeric substance of this embodiment, as repeating unit, have the represented repeating unit of formula (I), the represented repeating unit of preferred formula (I-a) gets final product, and these repeating units can contain more than a kind or 2 kinds.
In addition, polymkeric substance can also have formula (I) (preferred formula (the I-a)) repeating unit in addition more than a kind or 2 kinds.As formula (I) (preferred formula (I-a)) repeating unit in addition, the preferred represented repeating unit of formula V.Through also containing the represented repeating unit of formula V, can be with the solvability of polymkeric substance, mechanical, calorifics or electrology characteristic adjustment more suitable.In addition, the represented repeating unit of formula V also contains more than 2 kinds.
Figure BDA0000090305410000171
In the formula V, R 17And R 18Can be identical or different, the group of expression hydrogen atom, halogen atom or 1 valency.As the group of 1 valency, can use and above-mentioned same group.As R 17And R 18, preferred hydrogen atom, alkyl.
When combination contains the represented repeating unit of the represented repeating unit of formula (I) (preferred formula (I-a)) and formula V; Their ratio be preferably with respect to the former 100 moles; The latter is 10～1000 moles; It is 25～400 moles more preferably with respect to the former 100 moles of latter; Further preferred, be 50～200 moles with respect to the former 100 moles of latter.
As above-mentioned polymkeric substance, preferably have formula (VI)～(X), (IX-1), (X-1) represented repeating unit.The charge transfer property of these polymkeric substance is good especially.
Figure BDA0000090305410000181
Figure BDA0000090305410000191
Figure BDA0000090305410000201
In the formula, R 0, R 1, R 2, R 7, R 8, Z 1, Z 2And Z 3Respectively with above-mentioned synonym.In addition, the represented group of same-sign exists in molecule when a plurality of, and the represented group of same-sign each other can be identical or different.
In addition, when using the polymkeric substance of this embodiment as organic film, during terminal residual polymerisation reactivity group, characteristic, weather resistance during as organic thin film device reduce sometimes.Have under the situation of such worry, the polymerisation reactivity base can be used stable radical protection.
As polymkeric substance, special preferred formula (1)～(9) represented group.These polymkeric substance are except low LUMO and charge transfer property excellence, and the solvability in solvent is also very excellent.
Figure BDA0000090305410000211
Figure BDA0000090305410000221
Figure BDA0000090305410000231
Figure BDA0000090305410000241
Figure BDA0000090305410000251
In these formulas, R 1, R 2, R 7And R 8All with above-mentioned synonym.These groups exist in molecule when a plurality of, and the represented group of same-sign each other can be identical or different.In addition, p representes 1～20 integer, and q, r and s can be identical or different, the integer of expression 0～20.K representes the polymerization degree of polymkeric substance, suitable selection of formation method that can be when using the polymer formation organic film.When using the method formation organic film of the solution that coating forms polymer dissolution and organic solvent, k is preferably 3～500 integer, and more preferably 6～300 integer further is preferably 20～200 integer.In addition, obtain the inhomogeneity viewpoint of good film when utilizing coating film forming, the number-average molecular weight of the polystyrene conversion of polymkeric substance of the present invention is preferably 1 * 10 3～1 * 10 7, more preferably 1 * 10 4～1 * 10 6
[method of manufacture of polymkeric substance]
Below, to preferred embodiment describing of the method for manufacture of polymkeric substance.
Polymkeric substance can be by any means manufacturing, preferred especially following method of manufacture.For example, polymkeric substance preferably obtains by the following method: preparation formula (XI) and (XII) represented monomer as starting compound it is reacted.Thus, the polymkeric substance of the represented repeating unit of can obtain having formula well (I-a) represented repeating unit and formula V.In addition, this method of manufacture is an example, can suitably change according to the structure of the structure of subject polymer, starting compound, kind etc.
In the above-mentioned formula, Z 1, Ar 1, Ar 2, X, R 1, R 2, R 17, R 18, m and n all with above-mentioned synonym.
As the method that makes the represented monomer reaction of represented monomer of formula (XI) and formula (XII), can use Journal ofAmerican Chemical Society, vol.128 (2006) is the method for middle record p.3510..That is, can enumerate and in the presence of transition metal complex catalyst, make monomer reaction, make its initial ring polymeric method thus with non-conjugated diene.As transition metal complex catalyst, can using palladium diimine complex compound-four aromatic yl acid salt etc.Reaction times is preferably 0.5～150 hour.In addition, temperature of reaction is preferably between the boiling point of-10 ℃～solvent, more preferably 20～70 ℃.And then; As palladium diimine complex compound; Preferably [2-acenaphthylenediylidenebis (2 for N, N '-1; 4; 6-trimethylbenzenamine-.kappa.N)] chloromethyl-Palladium, [N, N '-1; 2-acenaphthylenediylidenebis[2,6-bis (1-methylethyl) benzenamine-.kappa.N)]] chloromethyl-Palladium.
When the material that polymkeric substance is used as organic thin film device used, its purity influenced element characteristic sometimes.Therefore, before above-mentioned reaction, preferably the monomer to starting compound distill, sublimation purifying, after the method for recrystallization etc. is made with extra care, carry out polymerization again.In addition, after the synthetic polymer, preferably carry out heavy making with extra care, Suo Shi extracts, based on purification process such as stratographic separation again.
As operable solvent in the reaction; Can enumerate pentane; Hexane; Heptane; Octane; Stable hydrocarbon such as hexanaphthene; Benzene; Toluene; Ethylbenzene; Unsaturated hydrocarbons such as xylenes; Tetracol phenixin; Chloroform; Methylene dichloride; Chlorobutane; N-butyl bromide; Chloropentane; Bromo pentane silane; Chlorohexane; Bromohexane; The chlorine hexanaphthene; Halo stable hydrocarbon such as bromine hexanaphthene; Chlorobenzene; Dichlorobenzene; Halo unsaturated hydrocarbons such as trichlorobenzene; Methyl alcohol; Ethanol; Propyl alcohol; Virahol; Butanols; Alcohols such as tertiary butyl alcohol; Formic acid; Acetate; Carboxylic-acids such as propionic acid; Dimethyl ether; Anaesthetie Ether; Methyl-tertbutyl ether; Tetrahydrofuran (THF); Ethers such as tetrahydropyrans diox, hydrochloric acid; Hydrogen bromide; Hydrofluoric acid; Sulfuric acid; Mineral acids such as nitric acid etc.Solvent can a kind uses separately, also can more than 2 kinds and use.
After the reaction, through using organic solvent extraction after the water cancellation, can obtain polymkeric substance through heating up in a steamer the common aftertreatment of desolvating etc.The separation of polymkeric substance with refining can be through separating based on stratographic and the method for recrystallization etc. is carried out.
[organic film]
Below, preferred embodiment organic film is described.The organic film of this embodiment contains the polymkeric substance with above-mentioned characteristic.
The thickness of organic film is preferably 1nm～100 μ m, more elects 2nm～1000nm as, further is preferably 5nm～500nm, is preferably 20nm～200nm especially.
Organic film can contain a kind of polymkeric substance of the present invention separately, also can contain polymkeric substance of the present invention more than 2 kinds.Organic film except the polymkeric substance that contains above-mentioned embodiment, can also contain electron transporting material, hole transport ability material in order to improve electron-transporting or hole transport ability.
As the hole transport ability material; Can use material known; For example can enumerate pyrazoline derivative, arylamines derivative, stilbene derivative, triaryl diamine derivative, oligo-thiophenes and derivative, Polyvinyl carbazole and derivative thereof, polysilane and derivative thereof, side chain or main chain has polyorganosiloxane ramification, polyaniline and derivative thereof, Polythiophene and derivative thereof, polypyrrole and derivative thereof, polyphenylene vinylene and the derivative thereof of aromatic amine or gathers inferior thienyl vinylidene and derivative thereof etc.
As electron transporting material; Can use material known, but for example metal complex, poly quinoline and derivative thereof, polyquinoxaline and the derivative thereof of Ju Chu oxadiazole derivative, anthraquinone bismethane and derivative, benzoquinones and derivative thereof, naphthoquinones and derivative thereof, anthraquinone and derivative thereof, four cyano anthraquinone bismethane and derivative thereof, fluorenone derivatives, phenylbenzene dicyano ethene and derivative thereof, diphenoquinone derivative, oxine and derivative thereof, gather fluorenes and derivative thereof, C 60In fullerene and derivative etc.
In addition, organic film produces electric charge in order to utilize the light that absorbs in the organic film, can contain charge generating material.As charge generating material, but illustration azo-compound and derivative thereof, diazonium compound and derivative thereof, metal-free phthalocyanine compound and derivative thereof, metal phthalocyanine compound and derivative 、 perylene compound thereof and derivative thereof, encircle quinone based compound and derivative, square hydrochlorate (Squarylium) compound and derivative thereof, Azulene (Azulenium) compound and derivative, thiapyran compound and derivative thereof, C more 60In fullerene and derivative etc.
And then organic film can contain the material of required other that are useful on the various functions of performance.As other material, can enumerate be used for to the function that the light that utilize to absorb produces electric charge carry out sensitizing sensitizing agent, be used to increase stability stabilization agent, be used to absorb the UV absorption agent of UV light etc.
In addition, organic film can contain polymkeric substance of the present invention macromolecular compound in addition as high polymer binder in order to improve the characteristic of machinery.As such high polymer binder, preferably excessively do not hinder the high polymer binder of charge transfer property or hole transport ability, and the preferred high polymer binder not strong to visible absorption.
As such high polymer binder; Can for example enumerate and gather (N-vinylcarbazole), polyaniline and derivative, Polythiophene and derivative thereof, gather (to phenylene vinylidene) and derivative thereof, gather (2, the inferior thienyl vinylidene of 5-) and derivative thereof, polycarbonate, polyacrylic ester, polymethyl acrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride, polysiloxane etc.
As the method for manufacture of the organic film of this embodiment, for example, can enumerate use solution of mixed polymer and electron transporting material as required or formation such as hole transport ability material, high polymer binder in solvent and carry out film forming method.In addition, when polymkeric substance of the present invention has sublimability, can form organic film through vacuum vapour deposition.
As the solvent that uses in the film forming of having used solution; As long as can make polymkeric substance; Electron transporting material; The hole transport ability material; Dissolving such as high polymer binder gets final product; Can enumerate toluene; Xylenes; Sym-trimethylbenzene; Tetraline; Naphthane; Dicyclohexyl; N-butylbenzene; Sec-butylbenzene; Unsaturated hydrocarbons series solvents such as tert.-butylbenzene; Tetracol phenixin; Chloroform; Methylene dichloride; Ethylene dichloride; Chlorobutane; N-butyl bromide; Chloropentane; Bromo pentane silane; Chlorohexane; Bromohexane; The chlorine hexanaphthene; The halogenated saturated hydrocarbon series solvent of bromine hexanaphthene etc.; Chlorobenzene; Dichlorobenzene; Halogenation unsaturated hydrocarbons series solvents such as trichlorobenzene, tetrahydrofuran (THF); Ethers series solvents such as tetrahydropyrans etc.Polymkeric substance of the present invention is according to its structure and molecular weight and meltage is different, but needs and can in these solvents, dissolve more than the 0.1 quality %.
As the film that uses solution, can use spin-coating method, casting method, nick version coating method, intaglio plate coating method, rod to be coated with method, rolling method, coiling rod and be coated with coating methods such as method, dip coating, spraying method, silk screen print method, flexographic printing method, offset printing method, ink jet printing method, divider print process, nozzle coating method and kapillary coating method.Wherein, preferred spin-coating method, flexographic printing method, ink jet printing method, divider print process, nozzle coating method and kapillary coating method.
In addition, in the operation of making organic film, can comprise the operation that makes polymer orientation of the present invention.Through this operation, the organic film that has been orientated polymkeric substance is because backbone molecule or side chain molecule are arranged to a direction, and therefore, charge migration degree or hole mobility improve sometimes.
As the method that makes polymer orientation, can use as the known method of the method for alignment of liquid crystal.Wherein rubbing manipulation, optical alignment method, shearing method (sliding stress applies method), to lift coating method easy and useful as method for alignment, is easy to utilize preferred rubbing manipulation, shearing method.
[organic thin film device]
The organic film of above-mentioned embodiment transmits property owing to contain the polymkeric substance of the present invention of above-mentioned embodiment so have excellent electric charge (electronics or hole).Therefore, this organic film can high efficiency of transmission from injected electrons or holes such as electrodes, or the electric charge that produces through photoabsorption etc. can be applicable to use the various electrical element (organic thin film device) of organic film.In addition, the polymkeric substance of the present invention of above-mentioned embodiment is owing to have the excellent trend of environmental stability, and therefore they form film through use, even in common atmosphere, and also can the stable organic thin film device of manufacturing property.Below, describe respectively for the example of organic thin film device.
(OTFT)
At first, preferred embodiment OTFT is described.OTFT can be to have source electrode and drain electrode, as the current path between them and the organic semiconductor layer that contains above-mentioned polymkeric substance (promptly; Active coating; As follows) and the structure of the gate electrode of the magnitude of current of control through current path, can the illustration field effect type, static induction type etc.
The field effect type OTFT preferably has: source electrode and drain electrode, as the current path between them and contain polymkeric substance organic semiconductor layer, the magnitude of current of control through current path gate electrode and between active coating and gate electrode the disposed insulation layer.Especially preferred source electrode and drain electrode and the organic semiconductor layer that contains polymkeric substance mutually ground connection and then the insulation layer that joins of clamping and organic semiconductor layer and gate electrode is set.
Static induction type OTFT preferably has: source electrode and drain electrode, as the current path between them and contain the organic semiconductor layer of polymkeric substance and the gate electrode of the magnitude of current of control through current path, and this gate electrode is arranged in the organic semiconductor layer.Particularly preferably, gate electrode that is provided with in source electrode, drain electrode and the organic thin film layer and the organic semiconductor layer that contains polymkeric substance ground connection setting mutually.As the structure of gate electrode, can be following structure: form from the source electrode to drain electrode mobile current path, and can enough magnitudes of current that flows through current path in the voltage control of gate electrode that adds, can enumerate for example comb shape electrode.
Fig. 1 is the diagrammatic cross-section of the OTFT (field effect type OTFT) that relates to of the 1st embodiment.OTFT 100 shown in Fig. 1 has: substrate 1, at the source electrode 5 and the drain electrode 6 that form with the interval of regulation on the substrate 1, cover source electrode 5 and drain electrode 6 and at the organic semiconductor layer 2 that forms on the substrate 1, at insulation layer 3 that forms on the organic semiconductor layer 2 and the gate electrode 4 that on insulation layer 3, forms with the mode in the zone that covers the insulation layer 3 between source electrode 5 and the drain electrode 6.
Fig. 2 is the diagrammatic cross-section of the OTFT (field effect type OTFT) that relates to of the 2nd embodiment.OTFT 110 shown in Fig. 2 has: substrate 1, the source electrode 5 that forms on the substrate 1, cover source electrode 5 and the organic semiconductor layer 2 that forms on the substrate 1, with source electrode 5 keep regulation the interval and at the drain electrode 6 that forms on the organic semiconductor layer 2, at insulation layer 3 that forms on organic semiconductor layer 2 and the drain electrode 6 and the gate electrode 4 that on insulation layer 3, forms with the mode in the zone of the insulation layer 3 between covering source electrode 5 and the drain electrode 6.
Fig. 3 is the diagrammatic cross-section of the OTFT (field effect type OTFT) that relates to of the 3rd embodiment.OTFT 120 shown in Fig. 3 has: substrate 1; The organic semiconductor layer 2 that on substrate 1, forms; The source electrode 5 and drain electrode 6 that on organic semiconductor layer 2, keep the interval formation of regulation; The part of covering source electrode 5 and drain electrode 6 and the insulation layer 3 that on organic semiconductor layer 2, forms; The gate electrode 4 that the mode that covers with a part with the zone of the zone of the insulation layer 3 that respectively bottom formed source electrode 5 and the insulation layer 3 that drain electrode 6 has been formed at the bottom forms on insulation layer 3.
Fig. 4 is the diagrammatic cross-section of the OTFT (field effect type OTFT) that relates to of the 4th embodiment.OTFT 130 shown in Fig. 4 has: substrate 1, at the gate electrode 4 that forms on the substrate 1, covering grid electrode 4 and the mode that covers at the insulation layer 3 that forms on the substrate 1, with the part in the zone of the insulation layer 3 that the bottom formed gate electrode 4 keeps the interval of regulation on insulation layer 3 and the source electrode 5 that forms and drain electrode 6 and the organic semiconductor layer 2 that on insulation layer 3, forms with the mode with the part covering of source electrode 5 and drain electrode 6.
Fig. 5 is the diagrammatic cross-section of the OTFT (field effect type OTFT) that relates to of the 5th embodiment.OTFT 140 shown in Fig. 5 has: substrate 1; The gate electrode 4 that on substrate 1, forms; Covering grid electrode 4 and the insulation layer 3 that on substrate 1, forms; The source electrode 5 that the mode that covers with the part in the zone of the insulation layer 3 that the bottom formed gate electrode 4 forms on insulation layer 3; The organic semiconductor layer 2 that the part of source electrode 5 is covered and on insulation layer 3, form; With mode that covers with a part and source electrode 5 with the zone of organic semiconductor layer 2 keep regulation the interval and on insulation layer 3 drain electrode 6 of formation.
Fig. 6 is the diagrammatic cross-section of the OTFT (field effect type OTFT) that relates to of the 6th embodiment.OTFT 150 shown in Fig. 6 has: substrate 1; The gate electrode 4 that on substrate 1, forms; Covering grid electrode 4 and the insulation layer 3 that on substrate 1, forms; The organic semiconductor layer 2 that the mode that covers with the zone of the insulation layer 3 that the bottom formed gate electrode 4 forms; The source electrode 5 that the mode that covers with the part with the zone of organic semiconductor layer 2 forms on insulation layer 3; With mode that covers with a part and source electrode 5 with the zone of organic semiconductor layer 2 keep regulation the interval and on insulation layer 3 drain electrode 6 of formation.
Fig. 7 is the diagrammatic cross-section of the OTFT (static induction type OTFT) that relates to of the 7th embodiment.OTFT 160 shown in Fig. 7 has: substrate 1; The source electrode 5 that on substrate 1, forms; The organic semiconductor layer 2 that on source electrode 5, forms; The a plurality of gate electrodes 4 that on organic semiconductor layer 2, keep the interval formation of regulation; With whole coverings of gate electrode 4 and the organic semiconductor layer 2a that on organic semiconductor layer 2, forms (constitute the material of organic semiconductor layer 2a can be identical also can be different) with organic semiconductor layer 2; With the drain electrode 6 that on organic semiconductor layer 2a, forms.
In the OTFT that the 1st～the 7th embodiment relates to, organic semiconductor layer 2 and/or organic semiconductor layer 2a contain polymkeric substance of the present invention, become the current path (raceway groove) between source electrode 5 and the drain electrode 6.In addition, gate electrode 4 is controlled the magnitude of current through the current path (raceway groove) among organic semiconductor layer 2 and/or the organic semiconductor layer 2a through impressed voltage.
Such field effect type OTFT can adopt known method, for example the method manufacturing of japanese kokai publication hei 5-110069 communique record.In addition, static induction type OTFT can adopt known method, for example the method manufacturing of TOHKEMY 2004-006476 communique record.
As substrate 1, as long as do not hinder characteristic, do not have special restriction as OTFT, can use film substrate, the plastic base of glass substrate, flexibility.
When forming organic semiconductor layer 2, with an organic solvent the way of soluble compound is highly beneficial and preferred on making in the equal solvent.And then, because the polymkeric substance of above-mentioned embodiment has high solvent borne to solvent, therefore, use the method for manufacture of the organic film of above-mentioned explanation, can form the organic film that becomes organic semiconductor layer 2 well.
Insulation layer 3 as joining with organic semiconductor layer 2 so long as the high material of electrical insulating property does not have special restriction, can use material known.Can enumerate for example SiOx, SiNx, Ta 2O 5, polyimide, polyvinyl alcohol, Vilaterm phenol, synthetic glass and photoresist material.From the viewpoint of low voltageization, the preferred high material of specific inductivity.
When on insulation layer 3, forming organic semiconductor layer 2; In order to improve the interfacial characteristics of insulation layer 3 and organic semiconductor layer 2, also can form organic semiconductor layer 2 after the surface modification again the surface of insulation layer 3 being handled with surface treatment agents such as silane coupling agents.As surface treatment agent, can enumerate for example silyl amine compound such as chain alkyl chlorosilane class, chain alkyl alkoxyl silicone alkanes, fluoro-alkyl chlorosilane class, fluoro-alkyl alkoxyl silicone alkanes, hexamethyldisilazane.Before handling with surface treatment agent, also can be in advance to surface of insulating layer with ozone UV, O 2Plasma body is handled.
In addition, after the making OTFT,, preferably on OTFT, form protective membrane for protecting component.Thus, OTFT and atmosphere are intercepted, can control the decline of the characteristic of OTFT.In addition, utilize protective membrane can reduce to form on the comfortable OTFT influence of the operation of driving display spare.
As the method that forms protective membrane, can enumerate and for example use UV cured resin, heat reactive resin or inorganic SiON XThe method that film covers.In order to carry out effectively and atmospheric obstruct, preferably to be exposed under the atmospheric situation (for example, in the exsiccant nitrogen atmosphere, vacuum in) until the operation that forms protective membrane after making OTFT and to carry out not making.
(solar cell)
Below, the application in solar cell describes to organic film of the present invention.Fig. 8 is the diagrammatic cross-section of the solar cell that relates to of embodiment.Solar cell 200 shown in Fig. 8 has: substrate 1, the organic semiconductor layer 2 that constitutes at the 1st electrode 7a that forms on the substrate 1, the organic film by containing above-mentioned polymkeric substance that on the 1st electrode 7a, forms and the 2nd electrode 7b that on organic semiconductor layer 2, forms.
In the solar cell of this embodiment, the side of the 1st electrode 7a and the 2nd electrode 7b uses transparent or semitransparent electrode.As electrode materials, can use metals such as aluminium, gold and silver, copper, basic metal, alkaline-earth metal or their semi-transparent film, nesa coating.In order to obtain high open circuit voltage,, preferably select with the big mode of difference change of work function as each electrode.In the organic semiconductor layer 2 (organic film),, can add charge generating in order to improve light sensitivity, sensitizing agent waits and uses.As base material 1, can use silicon substrate, glass substrate, plastic base etc.
(optical sensor)
Below, the application in optical sensor describes to organic film of the present invention.Fig. 9 is the diagrammatic cross-section of the optical sensor that relates to of the 1st embodiment.Optical sensor 300 shown in Fig. 9 has: substrate 1, the organic semiconductor layer 2 that constitutes at the 1st electrode 7a that forms on the substrate 1, the organic film by comprising above-mentioned polymkeric substance that on the 1st electrode 7a, forms, at charge generating layer 8 that forms on the organic semiconductor layer 2 and the 2nd electrode 7b that on charge generating layer 8, forms.
Figure 10 is the diagrammatic cross-section of the optical sensor that relates to of the 2nd embodiment.Optical sensor 310 shown in Figure 10 has: substrate 1, the organic semiconductor layer 2 that constitutes at the 1st electrode 7a that forms on the substrate 1, the charge generating layer 8 that on the 1st electrode 7a, forms, at the organic film by containing above-mentioned polymkeric substance that forms on the charge generating layer 8 and the 2nd electrode 7b that on organic semiconductor layer 2, forms.
Figure 11 is the diagrammatic cross-section of the optical sensor that relates to of the 3rd embodiment.Optical sensor 320 shown in Figure 11 has: substrate 1, the organic semiconductor layer 2 that constitutes at the 1st electrode 7a that forms on the substrate 1, the organic film by containing above-mentioned polymkeric substance that on the 1st electrode 7a, forms and the 2nd electrode 7b that on organic semiconductor layer 2, forms.
In the optical sensor that the 1st～the 3rd embodiment relates to, the side of the 1st electrode 7a and the 2nd electrode 7b uses transparent or semitransparent electrode.Charge generating layer 8 is absorb light and produce the layer of electric charge.As electrode materials, can use metals such as aluminium, gold and silver, copper, basic metal, alkaline-earth metal or their semi-transparent film, nesa coating.In order to improve light sensitivity, can add the current carrier propellant in the organic semiconductor layer 2 (organic film), sensitizing agent waits and uses.In addition, as base material 1, can use silicon substrate, glass substrate, plastic base etc.
[embodiment]
Below, describe in more detail according to embodiments of the invention and comparative example, but the present invention is not limited to these embodiment.
(condition determination)
At first, the condition of measuring in following embodiment and the comparative example is shown.
The trade(brand)name JMN-270 of nucleus magnetic resonance (NMR) wave spectrum use JEOL (NEC company) system ( 1270MHz when H measures), or the trade(brand)name JMNLA-600 of the said firm's system ( 19600MHz when F measures) measures.Chemical shift is represented with PPM (ppm).Interior mark 0ppm uses tetramethylsilane (TMS).Coupling constant (J) is with hertz (Hz) expression, and simple s, d, t, q, m and br represent unimodal (singlet), bimodal (doublet), triplet (triplet), quartet (quartet), multiplet (multiplet) and broad peak (broad) respectively.
In addition, the GCMS-QP5050A (trade(brand)name) of Shimadzu Scisakusho Ltd's system is used in mass analysis (MS), and through electron ionization (EI) method, or directly sample (DI) method that imports is measured.And then the silica gel during column chromatography is separated has used the trade(brand)name Silicagel 60N (40～50 μ m) of Northeast chemical company system.All chemical substances are SILVER REAGENT, from changing into industrial, Northeast chemical company, Nacalai tesque company, Sigma-Aldrich company or big aurification finished product company and buy with the pure pharmaceutical worker's industry of light company, Tokyo.
[embodiment 1]
Synthetic via compd A, B and the C shown in following made polymkeric substance D.
< synthesizing of compd A >
With reference to Khanh, L.P.; Dallemagne, P.; Rault, S.Synlett, 1999,9, the record of 1450-1452. is synthetic as 1 of starting raw material, and 3-two bromo-4H-encircle penta [c] thiophene-4,6 (5H)-diketone (compd A that following formula is represented).
Figure BDA0000090305410000341
< synthesizing of compd B >
(300mg 0.97mmol), dissolves it in THF (10mL) in the 100mL eggplant type flask, to add compd A.Add 1 therein, (0.43mL 2.91mmol), carries out stirring in 15 minutes at 70 ℃ 8-diazabicyclo [5,4,0]-11-7-alkene, and then (0.25mL 2.91mmol), carries out stirring in 4 hours at 70 ℃ to add the bromination allyl group.Add entry, behind the stopped reaction, extract with ethyl acetate.The washing organic layer, decompression is heated up in a steamer and is desolvated, and obtains solid.With the refining solid that obtains of column chromatography (silica gel, hexane: ethyl acetate=10: 1, volumetric ratio), obtain the represented compd B of following formula (220mg, yield 55%) with the faint yellow solid form.
The mensuration result of compd B is as described below.
TLC Rf=0.57 (10/1 hexane/ethyl acetate, volumetric ratio)
1H?NMR(400MHz，CDCl 3)δ2.52(d，4H，J＝7.6Hz)，5.01(d，2H，J＝10.2)，5.08(d，2H，J＝17.3Hz)，5.50-5.61(m，2H)
MS(EI)m/z?390(M +)
Figure BDA0000090305410000351
< synthesizing of Compound C >
(122mg 0.313mmol), dissolves it in toluene in test tube with cover, to add compd B.(292mg 0.782mmol), under nitrogen atmosphere, adds four (triphenylphosphines) and closes palladium (0), carries out stirring in 12 hours at 120 ℃ to add 2-tributyl tin thiophene therein.Subsequently, refining with column chromatography (silica gel, hexane: ethyl acetate=5: 1, volumetric ratio), obtain as the represented Compound C of the following formula of starting compound (93mg, yield 75%) with the form of yellow solid.
The mensuration result of Compound C is following.
TLC Rf=0.50 (10/1 hexane/ethyl acetate, volumetric ratio)
1H?NMR(400MHz，CDCl 3)δ2.57(d，4H，J＝7.6Hz)，4.97(d，2H，J＝11.7)，5.08(d，2H，J＝16.8Hz)，5.58-5.68(m，2H)，7.14(dd，2H，J＝3.6Hz，5.1Hz)，7.45(dd，J＝1.2Hz，5.1Hz)8.12(dd，J＝1.Hz，3.7Hz)
MS(EI)m/z396(M +).
< polymkeric substance D synthesizes 1 >
(60mg 0.151mmol), dissolves it in methylene dichloride in test tube with cover, to add Compound C.To wherein add the represented compd E of following formula (21mg, 0.0038mmol) and compound F 17-hydroxy-corticosterone (3.3mg, 0.0038mmol), room temperature carries out stirring in 48 hours.
Figure BDA0000090305410000362
Figure BDA0000090305410000371
After decompression is heated up in a steamer and desolvated, make thick resultant pass through silica gel with column chromatography (CHCl 3), use GPC (CHCl then 3) make with extra care.Consequently, obtain the represented polymkeric substance D (32mg) of following formula with the yellow solid form.In addition, the k among the following formula D representes the polymerization degree (following same).Polymkeric substance D shows high resolution to chloroform, methylene dichloride and tetrahydrofuran (THF).
The number-average molecular weight of the polystyrene conversion of the polymkeric substance D that obtains is 3100.In addition, the reduction potential of polymkeric substance D is-1.98V to show and hang down lumo energy that in addition, oxidizing potential is 0.90V.And then the mensuration result of other of polymkeric substance D is following.
1H?MR(400MHz，CDCl 3)δ0.88-1.33(broad)，6.77-7.22(broad)，7.26-7.50(broad)，7.77-8.16(broad)
Figure BDA0000090305410000381
[embodiment 2]
< Synthetic 2 of polymkeric substance D >
Replacement is carried out stirring in 48 hours in room temperature, stirs and be implemented in 40 ℃ 48 hours, in addition, likewise carries out the synthetic of polymkeric substance D with synthetic 1 of the polymkeric substance D of embodiment 1.Consequently, the number-average molecular weight that obtains polystyrene conversion is 3800 polymkeric substance D.
[embodiment 3]
< polymkeric substance D synthesizes 3 >
Replace compd E, use the represented compound M of following formula, in addition, likewise carry out the synthetic of polymkeric substance D with synthetic 1 of the polymkeric substance D of embodiment 1.Consequently, the number-average molecular weight that obtains polystyrene conversion is 3200 polymkeric substance D.
[embodiment 4]
< polymkeric substance D synthesizes 4 >
Replace carrying out under the room temperature stirring in 48 hours, stirred in 48 hours that are implemented in 40 ℃, in addition, likewise carry out the synthetic of polymkeric substance D with synthetic 3 of the polymkeric substance D of embodiment 3.Consequently, the number-average molecular weight that obtains polystyrene conversion is 3600 polymkeric substance D.
[embodiment 5]
Synthetic via compound G, H, J and the K shown in following made polymkeric substance L.
< compound G's is synthetic >
(300mg 0.968mmol), dissolves it in benzene (20ml) in the 50ml eggplant type flask, to add compd A.(1.08ml, 19.36mmol), (17mg 0.0968mmol), carries out stirring in 36 hours at 100 ℃ the tosic acid monohydrate to add terepthaloyl moietie therein.Add the water stopped reaction, extract, then, wash with ethyl acetate.Decompression is heated up in a steamer and is desolvated, and uses column chromatography (silica gel, 3/1 (volumetric ratio) hexane/ethyl acetate) to make with extra care then, obtains the represented compound G of following formula (348mg, yield 90%) with dark brown solid form.
The mensuration result of compound G is following.
TLC Rf=0.17 (3/1 hexane/ethyl acetate, volumetric ratio)
1H?NMR(400MHz，CDCl 3)δ2.81(s，2H，)，4.05-4.13(m，2H)，4.23-4.31(m，2H)
MS(EI)m/z398(M +).
Figure BDA0000090305410000401
< synthesizing of compound H >
(100mg 0.251mmol), dissolves it in THF in two mouthfuls of eggplant type flasks of 50ml, to add compound G.-78 ℃ add therein n-Butyl Lithium (the 1.6M hexane solution, 0.314ml, 0.502mmol).After 1 hour, (0.143ml 0.527mmol), slowly is warming up to room temperature to add tributyltin chloride with its stirring.After 2 hours, add the entry stopped reaction, extract with ethyl acetate.With the organic layer that water elution is got, use dried over mgso then.Subsequently, decompression is heated up in a steamer and is desolvated, and (aluminum oxide, 10/1 (hexane/ethyl acetate, volumetric ratio) made with extra care thick resultant, obtains the represented compound H of following formula (112mg, yield 55%) with the yellow liquid form with column chromatography.
The mensuration result of compound H is following.
TLC Rf=0.53 (10/1 hexane/ethyl acetate, volumetric ratio)
1H?NMR(400MHz，CDCl 3)δ0.83-0.93(m，18H)，1.01-1.18(m，12H)，1.27-1.37(m，12H)，1.51-1.67(m，10-H)，1.46-1.63(m，12H)，2.65(s，2H)，3.97-4.03(m，2H)，4.06-4.12(m，2H)
MS(EI)m/z818(M +).
Figure BDA0000090305410000411
< compound J's is synthetic >
Compound H, the represented compound I and four (triphenylphosphine) of following formula are closed palladium (0) and joined in the test tube with cover, it is dissolved in toluene.The limit is carried out heating edge to it and is stirred, and then, room temperature is transferred cold.Decompression is heated up in a steamer and is desolvated, and makes thick resultant through silica gel column chromatography, uses GPC (CHCl then 3) make with extra care.
Figure BDA0000090305410000412
The compound that obtains is joined in the eggplant type flask, it is dissolved in THF, add the vitriol oil therein, in stirring at room.Then, the reaction mixture that obtains is injected ice, extract, then, organic layer is washed, use dried over mgso then with saturated sodium bicarbonate aqueous solution and water with ethyl acetate.Then, decompression is heated up in a steamer and is desolvated, with GPC (CHCl 3) the refining solid that obtains, can obtain the represented compound J of following formula.
Figure BDA0000090305410000421
< synthesizing of compound K >
In the 100mL eggplant type flask, add compound J, it is dissolved in THF.Add 1 therein, 8-diazabicyclo [5,4,0]-11-7-alkene stirs while heat, and adds allyl bromide 98 again, heats while stirring.Add the water termination reaction, extract with ethyl acetate.The washing organic layer, decompression is heated up in a steamer and is desolvated.With the refining solid that obtains of column chromatography (silica gel), can obtain as the represented compound K of the following formula of starting compound.
< polymkeric substance L's is synthetic >
In test tube with cover, add compound K, it is dissolved in methylene dichloride.Add above-mentioned compd E and compound F 17-hydroxy-corticosterone therein, carry out under the room temperature stirring in 48 hours.Decompression is heated up in a steamer and is desolvated,
Make thick resultant through silica gel column chromatography (CHCl 3), use GPC (CHCl again 3) make with extra care, can obtain the represented polymkeric substance L of following formula.
[embodiment 6]
< making of OTFT and the evaluation of transistor characteristic thereof >
To in ethanol, distilled water, acetone, flood successively with the low-resistance silicon wafer (having the formation that becomes gate electrode/insulation layer) of heat oxide film (silicon oxide layer), carry out ultrasonic cleaning.Subsequently, this silicon wafer is carried out the UV-ozone clean, obtain the surface and be hydrophilic substrate.Under the room temperature, with this substrate at hexamethyldisilazane: flood in the chloroform, carry out ultrasonic cleaning, obtain surface treated substrate with chloroform.
Then, synthetic polymkeric substance D among the embodiment 1 is dissolved in the chloroform preparation coating solution.With this solution film forming on the surface-treated substrate, form organic film through spin-coating method.On this organic film, use metal mask to utilize vacuum evaporation to form gold electrode (source electrode, drain electrode), obtain OTFT.
Use analyzing parameters of semiconductor appearance (keithley corporate system; Trade(brand)name " 4200-SCS "); Make voltage Vsd variation between gate voltage Vg, source-leakage, the OTFT that obtains is measured the organic transistor characteristic, the result can obtain the Id-Vg characteristic of good n N-type semiconductorN.Can confirm that thus polymkeric substance of the present invention has excellent electric charge transmission property.
Description of reference numerals
1... substrate; 2... organic semiconductor layer; 2a... organic semiconductor layer; 3... insulation layer; 4... gate electrode, 5... source electrode, 6... drain electrode; 7a... the 1st electrode; 7b... the 2nd electrode, 8... charge generating layer, the OTFT of 100... the 1st embodiment; 110... the OTFT of the 2nd embodiment; 120... the OTFT of the 3rd embodiment, the OTFT of 130... the 4th embodiment, the OTFT of 140... the 5th embodiment; 150... the OTFT of the 6th embodiment; 160... the OTFT of the 7th embodiment, the solar cell of 200... embodiment, the optical sensor of 300... the 1st embodiment; 310... the optical sensor of the 2nd embodiment, the optical sensor of 320... the 3rd embodiment.

Claims (14)

1. polymkeric substance with the represented repeating unit of formula (I),
In the formula, Ar 0Expression can have substituent aromatic nucleus maybe can have substituent heterocycle, X 1And X 2Can be identical or different, expression Sauerstoffatom or sulphur atom.
2. polymkeric substance as claimed in claim 1, wherein,
The represented repeating unit of formula (I) is the represented repeating unit of formula (I-a),
Figure FDA0000090305400000012
In the formula, X 1And X 2With above-mentioned synonym, Ar 1And Ar 2Can be identical or different, the aromatic hydrocarbyl that expression can have the divalent of substituent carbon number more than 6 maybe can have the heterocyclic radical of the divalent of substituent carbon number more than 4; R 1And R 2Can be identical or different, the group of expression hydrogen atom, halogen atom or 1 valency; M and n can be identical or different, are 0～6 integer; Z 1Represent following formula (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) with (ix) represented group in any, the R in these formulas 3, R 4, R 5And R 6Can be identical or different, the group of expression hydrogen atom or 1 valency, R 3And R 4Can interosculate and form ring; The (iv) represented group of following formula can about counter-rotating; In addition, Ar 1Or Ar 2There are when a plurality of a plurality of Ar 1Or Ar 2Can be identical or different,
3. polymkeric substance as claimed in claim 2, wherein,
Said Ar 1With said Ar 2Can be identical or different, be the represented group of formula (II),
Figure FDA0000090305400000022
In the formula, R 7And R 8Can be identical or different, the group of expression hydrogen atom or 1 valency, R 7And R 8Can interosculate and form ring; Z 2Expression (xi), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii) and (xix) any in the represented group, the R in these formulas 9, R 10, R 11And R 12Can be identical or different, the group of expression hydrogen atom or 1 valency, R 9And R 10Can interosculate and form ring; The represented group of formula (xiv) can about counter-rotating,
Figure FDA0000090305400000031
4. like claim 2 or 3 described polymkeric substance, wherein,
Said Z 1Be the (ii) represented group of formula.
5. like claim 3 or 4 described polymkeric substance, wherein,
Said Z 2Be the represented group of formula (xii).
6. like each the described polymkeric substance in the claim 2～5, wherein,
Said R 1And R 2In at least one side be the represented group of formula (III),
Figure FDA0000090305400000032
In the formula, Ar 3The aromatic hydrocarbyl that expression can have substituent 3 valencys maybe can have the heterocyclic radical of substituent 3 valencys; Y 1And Y 2Can be identical or different, expression Sauerstoffatom, sulphur atom or the represented group of formula (a),
Figure FDA0000090305400000033
In the formula, A 1And A 2Can be identical or different, the group of expression hydrogen atom, halogen atom or 1 valency, and A 1And A 2In at least one for the group of electrophilic property.
7. polymkeric substance as claimed in claim 6, wherein,
The represented group of formula (III) is the represented group of formula (IV),
Figure FDA0000090305400000041
In the formula, Y 3And Y 4Can be identical or different, expression Sauerstoffatom, sulphur atom or the represented group of formula (a); R 0The group of expression hydrogen atom or 1 valency; J is to R from 1 0The integer that institute's bonded ring is had between can substituted positional number; R 0Exist when a plurality of, they can be identical or different; Z 3Expression (xxi), (xxii), (xxiii), (xxiv), (xxv), (xxvi), (xxvii), (xxviii) and (xxix) any in the represented group, the R in these formulas 13, R 14, R 15And R 16Can be identical or different, the group of expression hydrogen atom or 1 valency, R 13And R 14Can interosculate forms ring, the represented group of formula (xxiv) can about counter-rotating,
Figure FDA0000090305400000042
8. the represented monomer of a formula (XI),
Figure FDA0000090305400000051
In the formula, Ar 0Expression can have substituent aromatic nucleus maybe can have substituent heterocycle; X 1And X 2Can be identical or different, expression Sauerstoffatom or sulphur atom.
9. the represented monomer of a formula (XI-a),
Figure FDA0000090305400000052
In the formula, Ar 1And Ar 2Can be identical or different, the aromatic hydrocarbyl that expression can have the divalent of substituent carbon number more than 6 maybe can have the heterocyclic radical of the divalent of substituent carbon number more than 4; R 1And R 2Can be identical or different, the group of expression hydrogen atom, halogen atom or 1 valency; X 1And X 2Can be identical or different, expression Sauerstoffatom or sulphur atom; M and n can be identical or different, are 0～6 integer; Z 1Expression (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) with (ix) represented group in any, the R in these formulas 3, R 4, R 5And R 6Can be identical or different, the group of expression hydrogen atom or 1 valency, R 3And R 4Can interosculate and form ring; The (iv) represented group of formula can about counter-rotating; In addition, Ar 1Or Ar 2When a plurality of, a plurality of Ar 1Or Ar 2Can be identical or different,
Figure FDA0000090305400000061
10. organic film, it contains each the described polymkeric substance in the claim 1～7.
11. an organic thin film device, it has the described organic film of claim 10.
12. OTFT; It has source electrode, drain electrode, as the organic semiconductor layer of the current path between these electrodes and control gate electrode through the magnitude of current of said current path; Wherein, said organic semiconductor layer has the described organic film of claim 10.
13. an organic solar batteries, it has the described organic film of claim 10.
14. an optical sensor, it has the described organic film of claim 10.
CN2010800112702A 2009-03-11 2010-03-08 Polymer, organic thin film comprising the polymer, and organic thin-film element including same Pending CN102348728A (en)

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